US4987207A - Thermosetting resin compositions - Google Patents

Thermosetting resin compositions Download PDF

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Publication number
US4987207A
US4987207A US07/351,470 US35147089A US4987207A US 4987207 A US4987207 A US 4987207A US 35147089 A US35147089 A US 35147089A US 4987207 A US4987207 A US 4987207A
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groups
group
bis
carbon atoms
resin composition
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US07/351,470
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Norimasa Yamaya
Masahiro Ohta
Akihiro Yamaguchi
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Mitsui Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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Priority claimed from JP63118362A external-priority patent/JP2595038B2/ja
Priority claimed from JP63203717A external-priority patent/JPH07122002B2/ja
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37Thiols
    • C08K5/375Thiols containing six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415Five-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen

Definitions

  • thermosetting resin compositions that exhibit excellent heat resistance properties and are useful as adhesive films, laminating materials, and molding materials, and processes for preparing the same.
  • Polyimide resins have conventionally been used widely in the industry due to their excellent heat resistance, electrical insulating properties and chemical resistance properties.
  • condensation polyimide resins which are prepared via polyamic acids by reacting a tetracarboxylic dianhydride and a diamine in a polyimide resin, are among the many resins that exhibit excellent properties. They are however accompanied by disadvantages such as high softening points and poor processabilities.
  • a thermoplastic polyether imide that has improved processability at the sacrifice of some heat resistance (“Ultem”, trade mark; product of General Electric Company) has been known, its heat resistance and chemical resistance are less than satisfactory .
  • addition-type polyimide resins prepared by polymerizing bismaleimide compounds exhibit excellent thermal properties but are inferior in mechanical strength. It is therefore impossible to form them into films by casting.
  • the present invention overcomes the problems and disadvantages of the prior art by providing thermosetting resin compositions that exhibit superior properties.
  • thermosetting resin compositions that can be formed into films or the like prior to thermal curing and exhibit excellent toughness, flexibility, adhesion and heat resistance after thermal curing.
  • thermosetting resin composition comprising:
  • a bismaleimide compound selected from the group consisting of compounds of the formula (II): ##STR4## and compounds of the formula (III): ##STR5## wherein R 2 represents a divalent group selected from the group consisting of ##STR6## X is selected from the group consisting of a direct bond, divalent hydrocarbon groups having from about 1 to about 10 carbon atoms, hexafluorinated isopropylidene groups, carbonyl groups, thio groups, sulfinyl groups, sulfonyl groups and oxo groups.
  • the thermosetting resin composition of the invention contains as a polymer a polyamic acid obtained by reacting (a) a diamine compound represented by the formula (IV): ##STR7## wherein R 3 represents a divalent group selected from the group consisting of ##STR8## X is selected from the group consisting of direct bond, divalent hydrocarbon groups having from about 1 to about 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group and an oxo group, with (b) at least one tetracarboxylic dianhydride by a method known per se in the art; or (c) a polyimide obtained by dehydrating and cyclizing the polyamic acid.
  • Exemplary suitable diamine compounds include 1,3-bis(3-aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]s
  • a tetracarboxylic dianhydride is represented by the formula (V): ##STR9## wherein Y is a tetravalent group selected from the group consisting of aliphatic groups having at least two carbon atoms, cycloaliphatic groups, monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused cyclic aromatic groups composed of aromatic groups bonded together directly or via a crosslink.
  • Y represents a tetravalent group selected from the group consisting of aliphatic hydrocarbons having from 1 to 4 carbon atoms, cycloaliphatic hydrocarbons having from 4 to 8 carbon atoms, ##STR10## wherein X is selected from the group consisting of a direct bond, aliphatic hydrocarbons having from 1 to 4 carbon atoms, aliphatic hydrocarbons having from 1 to 4 carbon atoms substituted by from 1 to 6 fluorine atoms, --O--, --CO--, ##STR11##
  • Exemplary suitable tetracarboxylic dianhydrides include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-carboxyphenyl)sulfone dianhydr
  • N,N'-4,4'-Diphenylmethanebismaleimide represented by the formula (II) can be easily prepared by causing 4,4'-diaminodiphenylmethane and maleic anhydride to undergo a condensation and dehydration reaction in a manner known per se in the art.
  • bismaleimide compounds (III) useful in the practice of this invention include 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(3-maleimidophenoxy)phenyl]sulf
  • the bismaleimide compounds can be prepared easily by causing their corresponding diamine compounds and maleic anhydrides to undergo a condensation and dehydration reaction.
  • the bismaleimide compound may be used in an amount of from about 5 to about 100 parts by weight, preferably from about 10 to about 80 parts by weight per 100 parts by weight of the polymer of the formula (I). If the proportion of the bismaleimide compound is smaller than about 5 parts by weight, the bismaleimide compound cannot exhibit the effects of improving processability and mechanical properties, which are intended to be achieved in the present invention. On the other hand, amounts greater than about 100 parts by weight of the bismaleimide compound result in resin compositions which are brittle and have no formability and moldability.
  • the mixing of the polymer (I) and bismaleimide compound may be conducted in the form of powders, it is generally conducted by adding and dissolving the bismaleimide compound in a polymer varnish compound, preferably, in a polyamic acid and/or a polyimide varnish or suspension.
  • Exemplary solvents suitable for use in preparing the polymer varnish or suspension include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis(2- ⁇ 2-methoxyethoxy)ethyl ⁇ ether, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea and hexamethyl phosphoyl amide. These organic solvents may be used either singly or in combination.
  • the resin composition of the invention can be used as prepregs by having base materials such as glass cloths, carbon cloths or the like impregnated therewith, followed by drying.
  • the resin composition can be cast and dried on a glass plate, stainless steel plate or the like so that it can be used as a film-like adhesive free of any base material for various applications.
  • the drying temperature and time vary depending on the solvent employed and the kind of the bismaleimide used. However, it is necessary to maintain the temperature lower than the temperature at which marked polymerization of the bismaleimide compound begins to take place. The drying time must be long enough to reduce the content of the solvent to at least a level no affecting adversely the objects of this invention.
  • the resin composition can also be used as is, namely, in the form of powder as a molding material.
  • the curing time varies depending on the type of bismaleimide, tough and heat-resistant, molded articles can be obtained by heating and curing molded green products generally under an elevated pressure of from about normal pressure to about 1,000 kg/cm 2 at from about 150° to about 450° C. for from about 0.1 to about 10 hours.
  • the thermosetting resin composition of this invention may contain a polymerization catalyst if needed.
  • a polymerization catalyst if needed.
  • the catalyst is employed in an amount of from about 0.001 to about 10 wt. %, more preferably from about 0.1 to about 5 wt. % based on the total weight of the materials to be polymerized.
  • Conventional free radical catalysts such as benzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile and azobiscyclohexane carbonitrile are suitable for use as a polymerization catalyst. Two or more catalysts may be used in combination as needed.
  • thermosetting resin compositions of this invention are excellent in adhesion, formability, moldability, flexibility and heat resistance.
  • the thermosetting resin compositions have numerous applications including as adhesives, laminates and molding materials in electrical and electronic equipment and apparatus, and thus have significant industrial utility and advantages.
  • a vessel fitted with a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 73.6 g (0.2 mole) of 4,4'-bis(3-aminophenoxy)biphenyl and 467.2 g of N,N-dimethylacetamide.
  • 43.2 g (0.198 mole) of pyromellitic acid dianhydride were added in portions under a nitrogen gas atmosphere while paying attention to any increase of the temperature of the solution.
  • the resultant solution was stirred at room temperature for about 20 hours to obtain a polyamic acid varnish in N,N-dimethylacetamide as a solvent.
  • the varnish had a solution viscosity of 64 poises at 25° C. and a resin content of 20%.
  • the inherent viscosity of the polyamic acid thus obtained was 0.82 dl/g at 35° C. and had a 0.5% resin content.
  • N,N'-4,4'-diphenylmethanebismaleimide was added respectively in amounts given in Table 1, followed by the addition of N,N-dimethylacetamide to give a resin content of 20.0%.
  • the components thus added were dissolved at room temperature.
  • Each of the resin compositions thus prepared was cast on a glass plate and then dried at 130° C. for 1 hour and then at 180° C. for 2 hours, both, under a nitrogen gas atmosphere, thereby obtaining an uncured film 25 ⁇ m thick as a soft, brown and transparent film. By heating the uncured film at 250° C. for 30 minutes, a cured tough film was obtained.
  • Table 1 shows the softening points of those uncured films (as measured by the TMA penetration method) and their tensile shear strengths at 25° C. and a high temperature of 240° C. as measured in accordance with JIS-K-6848 and JIS-K-6850, namely, after separately inserting them between preheated steel sheets (cold rolled steel, JIS-3141, SPEC/SD, 25 ⁇ 100 ⁇ 1.6 mm) and bonding them to the associated steel sheets at 250° C. under 20 kg/cm 2 for 30 minutes.
  • a vessel fitted with a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 73.6 g (0.2 mole) of 4,4'-bis(3-aminophenoxy)biphenyl and 467.2 g of N,N-dimethylacetamide.
  • 43.2 g (0.198 mole) of pyromellitic acid dianhydride were added in portions under a nitrogen gas atmosphere while paying attention to any increase of the temperature of the solution.
  • the resultant solution was stirred at room temperature for about 20 hours to obtain a polyamic acid varnish in N,N-dimethylacetamide as a solvent.
  • the varnish had a solution viscosity of 64 poises at 25° C. and a resin content of 20.0%.
  • the inherent viscosity of the polyamic acid thus obtained was 0.82 dl/g at 35° C. and had a 0.5% resin content.
  • Table 1 shows the softening points of those uncured films (as measured by the TMA penetration method) and their tensile shear strengths at 25° C. and a high temperature of 240° C. as measured in accordance with JIS-K-6848 and JIS-K-6850, namely, after separately inserting them between preheated steel sheets (cold rolled steel, JIS-3141, SPEC/SD, 25 ⁇ 100 ⁇ 1.6 mm) and bonding them to the associated steel sheets at 250° C. under 20 kg/cm 2 for 30 minutes.
US07/351,470 1988-05-17 1989-05-15 Thermosetting resin compositions Expired - Lifetime US4987207A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP63118362A JP2595038B2 (ja) 1988-05-17 1988-05-17 熱硬化性樹脂組成物
JP63-118362 1988-05-17
JP63203717A JPH07122002B2 (ja) 1988-08-18 1988-08-18 熱硬化性樹脂組成物
JP63-203717 1988-08-18

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US4987207A true US4987207A (en) 1991-01-22

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US (1) US4987207A (de)
EP (1) EP0342912B1 (de)
KR (1) KR920004194B1 (de)
AU (1) AU620614B2 (de)
DE (1) DE68906459T2 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5200474A (en) * 1990-08-22 1993-04-06 Industrial Technology Research Institute Polyimide adhesive composition including barbituric acid modifier
US5401812A (en) * 1991-12-24 1995-03-28 Matsushita Electric Works, Ltd. Thermosetting polyimide composition, thermoset product thereof and manufacturing process thereof
US5460746A (en) * 1992-07-20 1995-10-24 Ube Industries, Ltd. Terminal-modified imide oligomer composition
US5470920A (en) * 1991-04-04 1995-11-28 Ciba-Geigy Corporation Impregnating solutions based on at least one reactive thermoplastic poly (imide-amide) oligomer and a coreactant, which can be used especially for the production of preimpregnated intermediate articles
US5608013A (en) * 1990-05-10 1997-03-04 Hitachi Chemical Company, Ltd. Polyimides and thermosetting resin compositions containing the same
US20040096679A1 (en) * 2002-11-14 2004-05-20 Mitsui Chemicals, Inc. Metal laminate
US20110281126A1 (en) * 2008-12-26 2011-11-17 Mitsuru Nozaki Resin composite copper foil

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU626940B2 (en) * 1988-10-28 1992-08-13 Advanced Elastomer Systems, L.P. Dynamically vulcanized alloys of crystalline polyolefin resin and halobutyl rubber material
EP0755979A3 (de) * 1993-04-02 1997-06-18 Hitachi Ltd Hitzehärtende Harzzusammensetzungen und ihre Verwendung von Dünnfilmleiterplatten

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4255313A (en) * 1979-04-20 1981-03-10 Gulf Oil Corporation Novel end-capped polyimide oligomers
US4362826A (en) * 1980-05-17 1982-12-07 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Heat-resistant resin composition
EP0107897A1 (de) * 1982-09-08 1984-05-09 Hitachi Chemical Co., Ltd. Polyamino-bis-imid-Harz
US4621122A (en) * 1984-06-05 1986-11-04 Minnesota Mining And Manufacturing Company High-temperature resistant electrically insulating coating powder
JPS63191810A (ja) * 1987-02-04 1988-08-09 Sumitomo Bakelite Co Ltd 低融点ビスマレイミド樹脂

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4255313A (en) * 1979-04-20 1981-03-10 Gulf Oil Corporation Novel end-capped polyimide oligomers
US4362826A (en) * 1980-05-17 1982-12-07 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Heat-resistant resin composition
EP0107897A1 (de) * 1982-09-08 1984-05-09 Hitachi Chemical Co., Ltd. Polyamino-bis-imid-Harz
US4621122A (en) * 1984-06-05 1986-11-04 Minnesota Mining And Manufacturing Company High-temperature resistant electrically insulating coating powder
JPS63191810A (ja) * 1987-02-04 1988-08-09 Sumitomo Bakelite Co Ltd 低融点ビスマレイミド樹脂

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, vol. 12, No. 275 (C 516) 3122 , Jul. 29, 1988 & JP A 63191810. *
Patent Abstracts of Japan, vol. 12, No. 275 (C-516) [3122], Jul. 29, 1988 & JP-A-63191810.
Patent Abstracts of Japan, vol. 12, No. 472 (C 551) 3319 , Dec. 9, 1988, p. 75, C 516 & JP A 6354435. *
Patent Abstracts of Japan, vol. 12, No. 472 (C-551) [3319], Dec. 9, 1988, p. 75, C 516 & JP-A-6354435.

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608013A (en) * 1990-05-10 1997-03-04 Hitachi Chemical Company, Ltd. Polyimides and thermosetting resin compositions containing the same
US5200474A (en) * 1990-08-22 1993-04-06 Industrial Technology Research Institute Polyimide adhesive composition including barbituric acid modifier
US5470920A (en) * 1991-04-04 1995-11-28 Ciba-Geigy Corporation Impregnating solutions based on at least one reactive thermoplastic poly (imide-amide) oligomer and a coreactant, which can be used especially for the production of preimpregnated intermediate articles
US5401812A (en) * 1991-12-24 1995-03-28 Matsushita Electric Works, Ltd. Thermosetting polyimide composition, thermoset product thereof and manufacturing process thereof
US5460746A (en) * 1992-07-20 1995-10-24 Ube Industries, Ltd. Terminal-modified imide oligomer composition
US20040096679A1 (en) * 2002-11-14 2004-05-20 Mitsui Chemicals, Inc. Metal laminate
US20110281126A1 (en) * 2008-12-26 2011-11-17 Mitsuru Nozaki Resin composite copper foil

Also Published As

Publication number Publication date
EP0342912B1 (de) 1993-05-12
EP0342912A1 (de) 1989-11-23
KR900003303A (ko) 1990-03-26
KR920004194B1 (ko) 1992-05-30
AU620614B2 (en) 1992-02-20
DE68906459T2 (de) 1994-01-05
DE68906459D1 (de) 1993-06-17
AU3490289A (en) 1989-11-23

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